WO1987006341A1 - Systemes d'analyse directe d'echantillons solides par spectroscopie d'emission atomique - Google Patents

Systemes d'analyse directe d'echantillons solides par spectroscopie d'emission atomique Download PDF

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Publication number
WO1987006341A1
WO1987006341A1 PCT/AU1987/000101 AU8700101W WO8706341A1 WO 1987006341 A1 WO1987006341 A1 WO 1987006341A1 AU 8700101 W AU8700101 W AU 8700101W WO 8706341 A1 WO8706341 A1 WO 8706341A1
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WO
WIPO (PCT)
Prior art keywords
spectral
lamp
sample
analysis
intensity
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Application number
PCT/AU1987/000101
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English (en)
Inventor
Michael Alfred Lucas
Terry Charles Hughes
Original Assignee
Chamber Ridge Pty. Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Chamber Ridge Pty. Ltd. filed Critical Chamber Ridge Pty. Ltd.
Publication of WO1987006341A1 publication Critical patent/WO1987006341A1/fr

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/67Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using electric arcs or discharges
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J2003/283Investigating the spectrum computer-interfaced
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/443Emission spectrometry

Definitions

  • This invention relates to systems for the direct analysis of solid samples by atomic emission spectroscopy.
  • spectroscopy for the analysis of samples is widely practised using atomic absorption, atomic emission or atomic fluorescence techniques in the spectroscopic analysis of a sample.
  • the most widely used elemental analysis techniques are atomic emission and atomic absorption and both techniques have well-known advantages and disadvantages. While the atomic absorption technique is relatively inexpensive, using simple instrumentation, performs rapid measurements, can be automated, is accurate and sensitive for many elements, and gives total elemental concentrations, little success has thus far been achieved in multi-elemental analysis, the sample must in most cases be in solution so that the technique is therefore destructive, elemental sensitivities vary from element to element, the technique is subject to sample matrix interference so that samples and standards must be matrix matched for accurate work, if the temperature of the flame is not sufficiently high, molecular spectral interference may occur due to incomplete sample break down, the technique is limited to operation in the visible region which eliminates its application to many electronegative elements and the concentration range covered is small (1 to 2 orders of magnitude) requiring sample dilution which can cause errors.
  • the major advantages include: the technique may be is truly multi-elemental and simultaneous in its operation, most elements can be measured using ultra violet-visible optics, a wide range of samples can be handled, concentration ranges of five orders of magnitude can be covered, instrumentation is relatively simple and reliable, the instruments can be automated, analytical sensitivity is high, complete sample break down occurs and interferences are restricted to those caused by spectral resolution limitations, and the technique has sub parts per million sensitivity.
  • the principal disadvantages of the atomic emission technique include the requirement for a thermally and physically stabilised high resolution spectrometer, the requirement for complete sample destruction, the matrix dependence of arc/spark analysis and the inaccuracies introduced thereby, the requirement for complete sample decomposition when using inductively coupled plasma which can be difficult with inert materials, the inability to distinguish between isotopes due to Doppler broadening, and the requirement for a power supply of the order of 10 kw.
  • the present invention provides an analysis system for analysis of samples by atomic emission spectroscopy comprising an atomic spectral lamp adapted to receive a solid sample to be analysed as a cathode of said spectral lamp; means for producing a primary electric discharge by cathodic sputtering from said sample, means for passing an inert gas through said spectral lamp; means for producing a secondary boosted discharge for analytical emission; spectral wave length analysis m ⁇ -ans arranged to receive and determine intensity of spectral lines emitted from said spectral lamp; and control means including means for controlling cathodic sputtering current used for generating said primary electric discharge from said sample and means for controlling operation of said spectral wave length analysis means, all on the basis of output parameters of said spectral wave length analysis means, whereby the cathodic sputtering current is controlled to maximise intensity of a spectral line of an element under investigation such that the relation between spectral line intensity and concentration of the element in said sample under investigation is maintained in a region
  • an atomic emission spectroscopy analysis method comprising locating a solid sample to be analysed as a primary cathode of an atomic spectral lamp; delivering a cathodic sputtering current to said sample for producing a primary electric discharge therefrom while passing an inert gas flow through said spectral lamp across said sample, means for producing a secondary discharge for analytical emission; arranging means for analysing spectral wave lengths to receive and determine intensity of spectral lines emitted from said spectral lamp, and controlling (i) cathodic sputtering current delivered to said sample; and (ii) operation of said spectral wave analysis means, all on the basis of output parameters of said spectral wave length analysis means, such that the relation between spectral line intensity and concentration of an element in the sample under investigation is maintained in a region which is substantially linear.
  • the spectral lamp employed in the practice of the present invention is preferably of the form described in Australian Patent Nos. 501,757 and 482,264 to the Commonwealth Scientific and Industrial Research Organization, and more particularly of the type manufactured under licence by S.G.E. Australia.
  • This spectral source has commonly been used for analysis using the atomic absorption technique and although it has been suggested by Lo dahl et al. (Analytica Chimica Acta, 148 [1983] 171-180) that the source may be used in emission spectroscopy, a practical system for achieving this form of analysis on a reproducable basis was not until the present invention achieved.
  • the lamp provides an extremely stable optical output.
  • the operating parameters of the lamp are easy to control using a small computer.
  • the system is relatively insensitive to minor changes in sample matrix composition.
  • the system is simple to operate and does not consume much power.
  • the system may be made in a portable form which may be of rugged construction, and
  • the lamp is preferably operated under the control of a small computer which controls not only the cathode current to allow control of the amount of material sputtered into the plasma in the required linear relationship with the cathode current but also controls the pressure of the inert gas, such as argon, which is fed to the lamp, the rate of flow of the inert gas and the temperature of the coolant which circulates through the lamp.
  • a small computer which controls not only the cathode current to allow control of the amount of material sputtered into the plasma in the required linear relationship with the cathode current but also controls the pressure of the inert gas, such as argon, which is fed to the lamp, the rate of flow of the inert gas and the temperature of the coolant which circulates through the lamp.
  • the system may be programmed to investigate any desired element of interest and after the sample is loaded into the lamp, a predetermined test sequence is performed under the control of the computer to produce the required results. Where the elements of the sample under test are unknown, the system may be caused to test the sample for a predetermied list of elements to determine the elements that are present and their concentrations.
  • the system is capable of performing isotopic. analyses for at least some lighter and heavier elements, and more particularly, many elements of interest in the analysis of geological samples.
  • the ability of the system to analyse for isotopes is believed to be due to the fact that the plasma which is formed by the boosted discharge in the lamp is not superheated so that Doppler broadening does not obscure the isotopic differences in wave number for heavier elements.
  • Fig. 1 is a schematic block diagram of the analysis system configured for atomic analysis
  • Fig. 2 is a schematic diagram showing the principal changes in the system of Fig. 1 for isotopic analysis
  • Fig. 3 is an exploded perspective view of a boosted demountable cathode lamp capable of use in the system of the present invention
  • Fig. 3A is an enlarged sketch of a sample holder and "cold finger" which is fitted to the boosted demountable cathode lamp generally shown in Fig. 3;
  • Fig. 4 shows typical data obtained by a system configured according to the invention (using a 3.4 M Ebert spectrometer) showing the spectra obtained for different standards at the same conditions, the ratio of copper powder to standard silver being as indicated in each case;
  • Fig. 5 shows the desired linear relationship
  • Fig. 6 shows the relationship between intensity and sputtering (cathode) current for two elements in different matrices; - .. Fig. 7 shows an early experimental result for an isotopic analysis;
  • Fig. 8 shows that changes in the cathode current have no effect on full width half maximum resolution
  • Fig. 9 shows the lack of effect on resolution due
  • spectral lamp 1 Central to the analysis system is spectral lamp 1 of having a demountable cathode of the general type described in Australian Patent Specification Nos. 482,264
  • the spectral lamp is driven by a suitable power source 2 under the control of a computer system 3.
  • the power supply provides a cathodic sputtering current via connection 8 and a boost current via connection 9.
  • sputtering current level is controlled in response to signal means via connection 10 from the computer system 3, whereas the boost current is set at a predetermined level and is controlled simply on an on/off basis via connection 11 from the computer system 3.
  • An inert gas such as argon (Ar) is
  • a vacuum pump (not shown) is also _ _ _
  • the spectral lamp 1 may also be provided with a coolant flow into the lamp via line 15 through a flow control valve 16. The coolant flow passing in heat exchange relation with the primary cathode of the lamp to enable temperature control thereof. The coolant is recirculated from the lamp via line 17 and a coolant temperature sensor 18 is provided to sense coolant temperature leaving the lamp 1.
  • Spectral emissions from the lamp 1 are directed along a light path 19 into spectral wave length analysis equipment 4 which may comprise, in one preferred arrangement, a 1M Czerny Turner 3500 Series Monochromator (A.R.L.) using a suitable defraction grating 5, such as a 4 inch 2400 lines/cm holographic grating, and having entrance and exit slits of suitable dimensions, for example, 20 ⁇ m.
  • the defraction grating 5 is mounted on a rotatable table which is rotated by a control motor 6 which is in turn controlled via connection 20 by the computer system 3.
  • a photomultiplier tube 7 is mounted at the exit slit from the analysis equipment 4 and its output is directed via connection 21 to an amplifier 22 where it is amplified and fed via connection 23 to an analog to digital converter ADCl.
  • a high voltage power supply 31 is provided for the photomultiplier tube 7 via connection 32.
  • a signal indicative of the argon gas pressure sensor is fed via connection 24 from the gas control pressure sensor 13 to an analog to digital converter ADC2.
  • a signal indicative of sputtering current level to the primary cathode of lamp 1 is delivered via connection 25 to an analog to digital converter ADC3 and a signal indicative of coolant temperature leaving the lamp 1 is delivered via connection 26 to an analog to digital converter ADC4.
  • the outputs of the analog to digital converters are then fed to the computer 27 of the computer system 3.
  • the computer 27 controls the sputtering current level (connection 10), the coolant flow rate by opening or closing the valve 16 via connection 28 and the inert gas pressure or flow rate via connections 29 and 30.
  • Stepping motors may preferably be used to control the vacuum pump (also not shown) for creating the flow rate of inert gas through the lamp 1.
  • stepping motors may be used to control the pressure (via a needle valve or the like) of the inert gas directed via line 12 to the lamp 1.
  • cathodic sputtering current may similarly be controlled by a stepping motor.
  • the foregoing control of cathodic sputtering current, inert gas flow rate and/or pressure and the coolant flow rate is all effected under control of the computer system 3 in response to signals received thereby. - ..
  • the use of stepping motors as aforesaid also leaves open the possibility of manual operation of each of these aspects.
  • the power supplies for the lamp 1 and the photomultiplier tube 7 are all standard control electronics (for example ARL) and need not be further described in the present specification.
  • the computer 3 may be any combination of the lamp 1 and the photomultiplier tube 7 .
  • the computer 3 controls the cathode current to the
  • the system ensures that there is not too much
  • the system can be returned to its desired linear relationship by reducing the cathode current which in turn reduces the amount of material which is being sputtered into the plasma. It is possible to check whether the output is in a desired linear region by following a routine of plotting output intensity against cathode current. For known sample matrices, the shape of this relationship should follow a fitted curve with the intensity increasing as cathode current increases (see Fig. 6).
  • the sample is formed into a small cylindrical pellet either by cutting and polishing the material itself (if the material is sufficiently conductive) or by crushing the sample into a fine powder and mixing it thoroughly with a conducting binding agent such as copper powder.
  • a conducting binding agent such as copper powder.
  • a mixture containing approximately 50% copper powder is usually satisfactory provided the mixture is thoroughly blended and then made into a pellet by pressing in a die according to a standard procedure.
  • FIGS 3 and 3A illustrate details of a suitable demountable cathode spectral lamp 1 for carrying out the present invention.
  • the sample prepared as aforesaid, forms the primary cathode 33 of the lamp.
  • the sample 33 is positioned on a holder 34 which in turn screws into a cold finger element 35.
  • a sleeve 36 is positioned over the sample 33 and the holder 34 with an insulating sleeve 37 being positioned thereover whereby only the outer end surface of the sample 33 is presented to the internal chamber of the lamp 1.
  • the element 35 screws into an insulating mount member 38 which in turn screws onto the main body 39 of the lamp 1 with the sample operationally positioned therein.
  • a coolant flow circulation is provided via lines 15,17 to flow through the cold finger element 35 to thereby control its temperature as well as the temperature of the sample 33.
  • the sample 33 is operationally located centrally and optically behind the window 40 which is made from optical quality silica.
  • an inert gas introduction pipe 12 and vacuum pipe connection 14 whereby inert gas flow may occur across the sample 33 and the window 40.
  • an anode 41 is provided and on the other side a secondary cathode in the form of a wound filament 42 is provided. Sputtering cathodic current is supplied via connection 8 to the sample 33 and boost current is supplied via connection 9 to the secondary cathode 42.
  • a "pump down, clean up" cycle is performed under the control of the computer 3.
  • the lamp is evacuated by means of the vacuum pump, the vacuum tap closed to see if the lamp is airtight (if the pressure rises a leak is present), the tap reopened and argon gas introduced into the system at a pressure of approximately 10 Torr to flush any contaminants out of the lamp. Vacuum is once again applied to clear the lamp and the above process is repeated three times.
  • the cathode current is then turned on to clean the surface of the sample and remove any contaminants from the sample.
  • the analysis procedure then begins.
  • the computer In analysing a sample having known elements, the computer is programmed to include a "shopping list" of elements and proceeds to analyse the sample for each of these elements in turn. For example, for a sample having unknown quantities of Fe, Ni, Cu, and S the sample would be mixed with an Ag powder binding agent and the system would be programmed to set the monochromator for to look at one of the Ag lines, such as 3382.89 A. The system would set the suitable starting conditions, for example, 2mA cathode current and 1.5 Torr argon gas pressure. The boost current is then activated to produce boosted glow discharge for approximately sixty seconds to clean the surface of the sample.
  • a "shopping list" of elements For example, for a sample having unknown quantities of Fe, Ni, Cu, and S the sample would be mixed with an Ag powder binding agent and the system would be programmed to set the monochromator for to look at one of the Ag lines, such as 3382.89 A. The system would set the suitable starting conditions, for example, 2mA cathode current and 1.5 Torr
  • the computer then increases the cathode current by 0.5mA and if the intensity of the spectral line detected by the photomultiplier tube 7 increases, the intensity of the output is measured and compared with tables in the computer to estimate if useful amounts of the element are being sputtered off. If not, the computer instructs the stepping motor to increase the cathode current. If a decrease in the output intensity is detected this means that self absorption is taking place and the cathode current is approximately halved and the monitoring procedure proceeds.
  • the computer takes the first element (Fe) from the shopping list and sets the monochromator 4 for that element, for example 3737.131A, and the output from the photomultiplier tube 7 is monitored against sputtering current to ensure that the element is being sputtered below a level at which self absorption occurs. If the. relationship is not linear, as described above, the cathode current is reduced by the computer and the analysis procedures continue. If the output is at a suitable level, the spectral line is scanned to build up statistics to preset levels, the peak is fitted and the computer checks its data store for standards and after correcting for the amount of binder used, places the result in the output file. The computer then proceeds to the next element in the shopping list and the procedure is repeated.
  • the monochromator 4 for that element, for example 3737.131A
  • each element in the shopping list is analysed in turn and a plot of spectral output against sputtering current is stored in the computer. Since the material is sputtered away from the sample in proportion to the elements present, all curves should be the same and where a curve starts to differ from the average, self absorption effects must be present and the cathode current must be reduced. Thus, the computer always takes data at a point which is well below any non-linear effects.
  • the monochromator is set at about 3,000 A and a scan procedure is commenced to build up a plot of output intensity against wave length from which spectral lines identifying the elements present in the sample may be extracted.
  • One method of achieving this is by locating spectral lines having a signal strength greater than three times the background signal, placing the wave length into a "line file” in the computer and then working through the "line file” comparing the wave lengths of the extracted lines with data tables to ascertain the elements present.
  • An output file showing the elements in order of increasing atomic weight is then created and a decision is made as to what elements in the sample should be more completely analysed according to the procedure described above.
  • the system shown in Fig. 1 of the drawings be modified in accordance with Fig. 2 of the drawings.
  • the monochromator is longer, for example a three to four metre Czerny Turner monochromator having a full width half maximum resolution of the order of 0.0025 at 4051 A, having a large defraction grating and an array detector 43 at the exit.
  • the array detector 43 is simply scanned to ascertain the intensity of each spectral line.
  • self-absorption will also increase the full width half maximum reoslution of a peak, so it is possible to watch the full width half maximum resolution with increasing cathode current to detect when self-absorption starts to occur.
  • isotopic analysis may also be performed using the system described in connection with Fig. 1 of the drawings.
  • the system according to the present invention is the only emission system which is capable of being used for isotopic analysis of heavy elements. This is believed to be due to the fact that the plasma produced by the boosted demountable cathode lamp is not super heated, due to the continual flow of argon through the lamp and the controlled cooling of the lamp, thereby preventing Doppler broadening which causes merging of the isotopic optical peaks which in turn means that the isotopic information is totally lost.
  • the absence of any Doppler broadening and the ability of this system to achieve isotopic analysis is clearly shown in Fig. 7 of the drawings in which the various isotopes of the lead sample under analysis may be clearly seen.
  • the system provides the principal advantage that solid samples may be analysed in a direct manner for elements and isotopes without the use of wet chemistry.
  • the system is also dynamic in that data is continually being gathered. and updated so that the measurements taken may be analysed against previously gathered data to give totally reproducable results.

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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract

Un système d'analyse, permettant d'analyser directement des échantillons solides par spectroscopie d'émission atomique, utilise une lampe spectrale atomique (1) du type permettant d'analyser un échantillon solide destiné à être disposé de façon démontable pour servir de cathode à la lampe (1), un dispositif (2) permettant de produire une première décharge électrique par pulvérisation cathodique depuis l'échantillon via une connexion (8) et une seconde décharge survoltée en vue de l'émission analytique via une connexion (9), un dispositif d'analyse de la longueur d'onde spectrale (4), destiné à recevoir et à déterminer l'intensité des lignes spectrales émises par la lampe (1), et un dispositif de commande (3) du système, le niveau de courant de la cathode de l'échantillon et le fonctionnement du dispositif d'analyse de longueur d'onde spectrale (4) étant régulés sur la base de la sortie provenant du tube photomultiplicateur (7), de telle sorte que l'intensité des lignes spectrales est maximalisée et la relation entre l'intensité des lignes spectrales et la concentration de l'élément correspondant dans l'échantillon sont maintenues dans une région essentiellement linéaire.
PCT/AU1987/000101 1986-04-16 1987-04-15 Systemes d'analyse directe d'echantillons solides par spectroscopie d'emission atomique WO1987006341A1 (fr)

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AUPH548186 1986-04-16
AUPH5481 1986-04-16

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US (1) US4824249A (fr)
EP (1) EP0264397A4 (fr)
CA (1) CA1261486A (fr)
WO (1) WO1987006341A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0396291A2 (fr) * 1989-04-29 1990-11-07 FISONS plc Procédé et appareil pour spectroscopie d'émission optique
EP0407030A1 (fr) * 1989-05-31 1991-01-09 Clemson University Procédé et appareil d'analyse d'échantillons solides
EP0437358A2 (fr) * 1990-01-10 1991-07-17 FISONS plc Spectrométrie à décharge lumineuse
US5325021A (en) * 1992-04-09 1994-06-28 Clemson University Radio-frequency powered glow discharge device and method with high voltage interface

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5253183A (en) * 1988-01-06 1993-10-12 Hitachi, Ltd. Obtaining a spectrogram from a single scanning of interference fringes
US5023804A (en) * 1989-05-23 1991-06-11 The Perkin-Elmer Corporation Method and apparatus for comparing spectra
GB9316742D0 (en) * 1993-08-12 1993-09-29 Univ Waterloo Imtroduction of samples do inductively coupled plasma
US7368710B2 (en) * 2000-02-09 2008-05-06 Xceleron Limited Sample preparation method
FR2826121B1 (fr) * 2001-06-18 2004-02-20 Jobin Yvon Sas Dispositif et procede de positionnement d'un echantillon monte sur un spectrometre a decharge luminescente
US7273998B2 (en) * 2004-09-15 2007-09-25 General Electric Company System and method for monitoring laser shock processing
DE102005057919B4 (de) * 2005-12-02 2021-01-21 Spectro Analytical Instruments Gmbh Vorrichtung zur Analyse einer Festkörperprobe und Betriebsverfahren
US7733482B2 (en) * 2007-03-26 2010-06-08 Ruda Harry E System and method for determining at least one constituent in an ambient gas using a microsystem gas sensor
CN101458212B (zh) * 2009-01-04 2011-01-26 北京心润心激光医疗设备技术有限公司 实时成像的光学相干层析皮肤诊断设备
DE102009018253A1 (de) * 2009-04-21 2010-11-11 OBLF, Gesellschaft für Elektronik und Feinwerktechnik mbH Verfahren und Vorrichtung zur spektrometrischen Elementanalyse
US9536725B2 (en) 2013-02-05 2017-01-03 Clemson University Means of introducing an analyte into liquid sampling atmospheric pressure glow discharge
CN105136775A (zh) * 2015-09-25 2015-12-09 内蒙古包钢钢联股份有限公司 一种辉光光谱仪测定镀锌板基体各元素含量的方法
CN105181676A (zh) * 2015-09-29 2015-12-23 内蒙古包钢钢联股份有限公司 一种辉光光谱仪测定镀锌板镀层深度和镀层质量的方法
DE102016200517A1 (de) * 2016-01-18 2017-07-20 Robert Bosch Gmbh Mikroelektronische Bauelementanordnung und entsprechendes Herstellungsverfahren für eine mikroelektronische Bauelementanordnung
CN110402385A (zh) * 2016-12-15 2019-11-01 美国杰莫洛吉克尔研究所有限公司 用于筛选宝石的装置和方法
JP6765328B2 (ja) 2017-03-15 2020-10-07 株式会社堀場製作所 作成方法、グロー放電発光分析方法、器具、及びグロー放電発光分析装置
US10859505B2 (en) * 2018-01-26 2020-12-08 Gemological Institute Of America, Inc. (Gia) Fluorescence box for gemological applications

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097781A (en) * 1974-11-27 1978-06-27 Hitachi, Ltd. Atomic spectrum light source device
AU2560177A (en) * 1976-06-07 1978-11-30 Commonwealth Scientific And Industrial Research Organisation High intensity atomic spectral lamp
US4462685A (en) * 1981-03-04 1984-07-31 Instrumentation Laboratory Inc. Spectroanalytical system

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU407994B2 (en) * 1968-05-01 1970-11-06 Commonwealth Scientific And Industrial Research Organisation Improvements in or relating to spectroscopy and colorimetry
JPS4821313B1 (fr) * 1968-05-15 1973-06-27
NL6812602A (fr) * 1968-09-04 1970-03-06
DE2341204A1 (de) * 1972-08-18 1974-02-28 Commw Scient Ind Res Org Vorrichtung zur durchfuehrung von spektralanalysen
US4128336A (en) * 1975-08-21 1978-12-05 The South African Inventions Development Corporation Spectroscopic apparatus and method
JPS5628458A (en) * 1979-08-17 1981-03-20 Hitachi Ltd Atomic spectrum generating lamp

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097781A (en) * 1974-11-27 1978-06-27 Hitachi, Ltd. Atomic spectrum light source device
AU2560177A (en) * 1976-06-07 1978-11-30 Commonwealth Scientific And Industrial Research Organisation High intensity atomic spectral lamp
US4462685A (en) * 1981-03-04 1984-07-31 Instrumentation Laboratory Inc. Spectroanalytical system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Applied Spectroscopy, Volume 32, Number 3, 1978, T. C. WOLFE et al; "Optimization of Pulsing Conditions for Hollow Cathode Lamps for Atomic Fluorescence Spectrometry" pp 265-268 *
Spectroscopy Letters Volume 10, Number 9, 1977, pp 727-736, R. B. DJULGEROVA "Spectroscopical Effects Arising under Application of Pulse Supply to Zinc Hollow Cathode Discharge" *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0396291A2 (fr) * 1989-04-29 1990-11-07 FISONS plc Procédé et appareil pour spectroscopie d'émission optique
EP0396291A3 (fr) * 1989-04-29 1991-07-31 FISONS plc Procédé et appareil pour spectroscopie d'émission optique
EP0407030A1 (fr) * 1989-05-31 1991-01-09 Clemson University Procédé et appareil d'analyse d'échantillons solides
EP0437358A2 (fr) * 1990-01-10 1991-07-17 FISONS plc Spectrométrie à décharge lumineuse
EP0437358A3 (en) * 1990-01-10 1992-05-13 Vg Instruments Group Limited Glow discharge spectrometry
US5184016A (en) * 1990-01-10 1993-02-02 Vg Instruments Group Limited Glow discharge spectrometry
US5325021A (en) * 1992-04-09 1994-06-28 Clemson University Radio-frequency powered glow discharge device and method with high voltage interface

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EP0264397A1 (fr) 1988-04-27
US4824249A (en) 1989-04-25
CA1261486A (fr) 1989-09-26
EP0264397A4 (fr) 1989-05-30

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